JP7130782B2 - Modified conjugated diene polymer and method for producing the same - Google Patents

Description

[Cross reference to related applications]
This application claims the benefit of priority based on Korean Patent Application No. 10-2018-0167686 dated December 21, 2018, and all contents disclosed in the documents of the Korean Patent Application are incorporated herein by reference. included as a part.

TECHNICAL FIELD The present invention relates to a modified conjugated diene-based polymer modified with a polyfunctional acrylate-based modifier at least one end and having high processability, compoundability and low cold flowability, and a method for producing the same.

Recently, with the growing interest in energy saving and environmental issues, there is a demand for low fuel consumption of automobiles. As one of the methods for realizing this, a method has been proposed in which inorganic fillers such as silica or carbon black in the tire-forming rubber composition are used to reduce the heat build-up of the tire. Since it is not easy to disperse the inorganic filler, there is a problem in that physical properties of the rubber composition such as wear resistance, crack resistance, workability, etc. are generally deteriorated.

In order to solve such problems, as a method for increasing the dispersibility of inorganic fillers such as silica or carbon black in rubber compositions, conjugated diene polymers obtained by anionic polymerization using organic lithium A method was developed to modify the polymerization active sites of , into functional groups capable of interacting with inorganic fillers. Specifically, a method of modifying the polymerization active terminal of the conjugated diene-based polymer with a tin-based compound, a method of introducing an amino group, a method of modifying with an alkoxysilane derivative, or the like has been proposed.

However, when a rubber composition is produced using a conjugated diene polymer modified by the above-described method, although low heat build-up can be ensured, the effect of improving the physical properties of the rubber composition, such as abrasion resistance and processability, is limited. it wasn't enough.

As another method, a method has been developed in which the living active terminal of a living polymer obtained by coordination polymerization using a catalyst containing a rare earth metal compound is modified with a specific coupling agent or modifying agent. However, a modified conjugated diene-based polymer such as polybutadiene produced using a catalyst containing a rare earth metal compound has a high 1,4-cis content, a high molecular weight, and a narrow molecular weight distribution, thereby improving tire rolling characteristics. Although it exhibits excellent physical properties, it can cause storage problems due to poor processability and high cold flow.

Cold flowability is a physical property that affects the storability, workability, and processability of a polymer, and the initial shape of the polymer is pushed and deformed by the weight of the polymer during storage. characterize. Since the product specification cannot be maintained as high as the cold flow property, the storage stability and workability may be deteriorated due to requantification, and in serious cases, it may lead to product contamination and disposal. Cold flowability is higher in polymer compositions that are blended by adding oil to polymers to improve processability, and upward control of Mooney viscosity and degree of polymerization is very important for such products. is.

US Pat. No. 5,567,784A discloses a method for adding sulfur chloride after the production of 1,4-cis-polybutadiene and a method for removing unreacted butadiene and low boilers to solve the odor problem. However, it is difficult to completely remove the odor caused by sulfur because sulfur chloride is added later. KR10-0472649B1 discloses a method of adding an organic borane compound such as triethylborane to the reaction system after a certain period of time has passed after polymerization in order to improve cold flowability. (boiling point: about −20° C.) and that it must be handled with care in the absence of oxygen and moisture due to the danger of explosion. _EP0386808A1 attempts to improve the cold flowability by adding PCl3 before terminating the polymerization, but it has the characteristic that the Mooney viscosity changes greatly even with a small amount and is difficult to control. No. 5,064,910A attempts to increase the molecular weight distribution of the polymer by adding tin halide to the polymer to improve the cold flowability and physical properties, but modification with tin causes the chemical bond between carbon and tin to become a processing additive. and can be weakened over time by environmental factors, and have inherent heavy metal contamination problems.

In addition to the problem of bad odor caused by additives, the conventional techniques as described above have problems such as weak binding force between the modifier-derived group and the active polymer, reduction of 1,4-cis content, limit of improvement in cold flow property, and control of Mooney viscosity. have limits.

US5567784A (1996.10.22) KR10-0472649B1 (2004.05.31) EP0386808A1 (1990.09.12) US5064910A (1991.11.12) US5064910A (1991.11.12)

DISCLOSURE OF THE INVENTION The present invention was devised to solve the problems of the prior art described above, and the cold flow property is improved by lowering the beta value that affects the cold flow property through the adjustment of the degree of branching. An object of the present invention is to provide a modified conjugated diene-based polymer which can be efficiently controlled, improved in processability, and adjusted in degree of polymerization and increase in Mooney viscosity.

Another object of the present invention is to provide a method for producing the modified conjugated diene polymer.

A further object of the present invention is to provide a rubber composition containing the modified conjugated diene polymer.

In order to solve the above problems, the present invention provides a modified conjugated diene-based polymer represented by the following chemical formula 1, in which the polymer chain end is modified.

In the chemical formula 1,
A may be a hydrocarbon unit having 2 to 12 carbon atoms or a hydrocarbon unit having 2 to 12 carbon atoms containing one or more heteroatoms selected from N or O;
R _x may be hydrogen or a methyl group,
n may be an integer from 2 to 6.

The present invention also provides a modified conjugated diene polymer having a beta value of 0.21 or less.

Further, the present invention comprises the steps of: 1) polymerizing a conjugated diene-based monomer in the presence of a catalyst composition containing a rare earth metal compound to prepare an active polymer to which an organic metal is bound; and reacting the coalescence with a modifier represented by Formula 2 below.

In the chemical formula 2,
A may be a hydrocarbon unit having 2 to 12 carbon atoms or a hydrocarbon unit having 2 to 12 carbon atoms containing one or more heteroatoms selected from N or O;
R _x may be hydrogen or a methyl group,
n may be an integer from 2 to 6.

The present invention also provides a rubber composition containing the modified conjugated diene polymer.

The modified conjugated diene-based polymer according to one embodiment of the present invention has a polymer chain end modified and has a structure represented by Chemical Formula 1, so that a strong carbon-carbon bond is formed between polymer chains. can have terminal cross-links linked with , which can effectively control cold flowability by lowering the beta value through adjusting the degree of branching of the polymer, greatly improving processability, and strong Cross-linking is formed by carbon-carbon bonds, and the deterioration of the polymer over time due to various additives that may be added during compounding of the rubber composition can be suppressed.

In addition, the modified conjugated diene-based polymer according to one embodiment of the present invention can maintain the linearity in the chain of the polymer by containing a modifier-derived group at the end, so that excellent physical properties can be secured. The degree of branching is adjusted by cross-linking between polymer chains to adjust the degree of polymerization and the rate of increase in Mooney viscosity before and after modification. Formulation properties such as properties and viscoelastic properties can be improved.

Hereinafter, the present invention will be described in more detail in order to deepen the understanding of the present invention.

Terms and words used in the specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventors are responsible for describing their invention in the best possible way. , should be interpreted as meanings and concepts that conform to the technical idea of the present invention, in accordance with the principle that the concepts of terms can be defined appropriately.

[the term]
As used herein, the term "preforming" means pre-polymerization within a conjugated diene polymerization catalyst composition. Specifically, the catalyst composition for conjugated diene polymerization containing a rare earth metal compound, an alkylating agent containing an aluminum compound, and a halogen compound contains diisobutyl aluminum hydride (hereinafter referred to as DIBAH) as the aluminum compound. When containing such an aluminum hydride-based compound, a small amount of a monomer such as butadiene is also contained in order to reduce the possibility of generating various catalytically active species. Accordingly, prior to the polymerization reaction for producing the conjugated diene-based polymer, pre-polymerization of butadiene is performed in the catalyst composition for producing the conjugated diene-based polymer, which is called pre-polymerization.

Also, as used herein, the term "premixing" means a state in which each component is uniformly mixed without polymerization within the catalyst composition.

Also, as used herein, the term "catalyst composition" includes simple mixtures of the components, various complexes or chemical reactions of the components brought about by physical or chemical attraction.

As used herein, the term "alkyl group" may mean a monovalent saturated aliphatic hydrocarbon, including straight chain alkyl groups such as methyl, ethyl, propyl and butyl, and isopropyl , sec-butyl, tert-butyl and neo-pentyl may all be included.

[Measuring method]
In the present invention, the "Mooney viscosity (MV)" is a scale for judging the workability of a polymer, and when the Mooney viscosity is low in the proper line, the flow is good and it is judged that the workability is excellent. , The unit is MU (Mooney Unit), and the ML (1 + 4) value was obtained at 100 ° C., where M is Mooney, L is the size of the plate, and 1 is the preheating time 1 minute and 4 indicates that the value was read 4 minutes after the rotor was activated.

Specifically, the Mooney viscosity was measured by using MV2000E (Monsanto), using a Large Rotor at 100°C with Rotor Speed 2 ± 0.02 rpm, and leaving the polymer at room temperature (23 ± 5°C) for 30 minutes or more. ±3 g was taken and placed inside the die cavity and measured while the platen was actuated and torque was applied.

In the present invention, "molecular weight distribution (PDI; MWD, Mw/Mn)" indicates the degree of molecular weight distribution of the polymer, and the ratio of the weight average molecular weight (Mw) to number average molecular weight (Mn) of the polymer (Mw /Mn). The weight average molecular weight and number average molecular weight were measured using gel permeation chromatography (GPC) after dissolving the polymer in tetrahydrofuran (THF) at 40° C. for 30 minutes. uses a combination of two PLgel Olexis columns (trade name of Polymer Laboratories) and one PLgel mixed-C column, and the new replacement columns are all mixed bed type columns. Polystyrene was used as a permeation chromatography standard material (GPC Standard material).

In the present invention, the "beta-value" is a function of frequency and indicates the degree of branching of the polymer. A smaller value indicates an increased degree of branching and a larger value indicates a decreased degree of branching. Specifically, the beta value is measured using a D-RPA 3000 (rubber process analyzer) manufactured by Montetech, with a frequency sweep range of 0 to 100 Hz and static strain. 3%, dynamic strain 0.25%, tan δ is measured at a measurement temperature of 100 ° C. d (log (tan δ)) / d (log (freq)) slope is taken as beta value (β-value) Indicated. Here, tan δ is a value indicated by the ratio of the viscosus modulus (G'') to the elastic modulus (G') as an index indicating general viscoelastic properties.

According to one embodiment of the present invention, there is provided a modified conjugated diene-based polymer represented by the following Chemical Formula 1, in which the ends of polymer chains are modified.

In the chemical formula 1,
A may be a hydrocarbon unit having 2 to 12 carbon atoms or a hydrocarbon unit having 2 to 12 carbon atoms containing one or more heteroatoms selected from N or O;
R _x may be hydrogen or a methyl group,
n may be an integer from 2 to 6.

Specifically, in Chemical Formula 1, the hydrocarbon unit having 2 to 12 carbon atoms may be an unit represented by Chemical Formula 3 below.

[Chemical Formula 3]
*-R _a1 -*
In the chemical formula 3,
R _a1 may be a linear or branched alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms;
* is the position to which the (meth)acrylate-derived group of Chemical Formula 1 is bonded.

Further, in Chemical Formula 1, the hydrocarbon unit having 2 to 12 carbon atoms containing at least one heteroatom of N or O is represented by the following Chemical Formulas 4-1 to 4-4: Any one of them may be used.

[Chemical Formula 4-1]
(R _b1 ) ₃ C-R _b2 -OR _b3 -C(R _b4 ) _m1 (R _b5 ) _3-m1
In the chemical formula 4-1,
R _b1 and R _b4 may each independently be an alkyl group having 1 to 5 carbon atoms, and the (meth)acrylate-derived group of the chemical formula 1 may be bound to the end,
R _b2 and R _b3 may each independently be an alkylene group having 1 to 5 carbon atoms,
R _b5 may be a hydroxy group,
_m1 may be an integer from 1 to 3;
[Chemical Formula 4-2]
C(R _c1 -OR _c2 ) _m2 (R _c3 ) _4-m2
In the chemical formula 4-2,
R _C1 may be an alkylene group having 1 to 6 carbon atoms,
R _C2 may be an alkyl group having 1 to 6 carbon atoms, and the (meth)acrylate-derived group of the chemical formula 1 may be bonded to the terminal,
R _c3 may be hydrogen or an alkyl group having 1 to 6 carbon atoms,
_m2 may be an integer from 1 to 4;
[Chemical Formula 4-3]
C(R _d1 ) _m3 (R _d2 ) _4-m3
In the chemical formula 4-3,
R _d1 may be an alkyl group having 1 to 6 carbon atoms, and the (meth)acrylate-derived group of the chemical formula 1 may be bonded to the end,
R _d2 may be a hydroxy group or an alkyl group having 1 to 6 carbon atoms,
_m3 may be an integer from 1 to 4;

In the chemical formula 4-4,
R _e1 to R _e3 may each independently be an alkylene group having 1 to 5 carbon atoms,
* is the position to which the (meth)acrylate-derived group of Chemical Formula 1 is bonded.

Here, the (meth)acrylate-derived group in Chemical Formula 1 represents a (meth)acrylate group to which a polymer chain is bonded. Specifically, in Chemical Formulas 3 to 4-3, (Meth)acrylate-derived group is bound to indicate that the end of the hydrocarbon unit is bound to the polymer--CH ₂ CHR _x COO-- of chemical formula (1). In Chemical Formula 4-4, * indicates the position where polymer--CH ₂ CHR _x COO-- in Chemical Formula 1 is bound.

More specifically, the modified conjugated diene polymer includes dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, propoxylated glycerol triacrylate, tri methylolpropane ethoxylate triacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, 1,2-ethanediol diacrylate, neopentyl glycol diacrylate, 1,3-butanediol diacrylate, 1 , 4-phenylenediacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol hydroxypentamethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, trimethylolpropane trimethacrylate, propoxylated glycerol trimethacrylate, trimethylolpropane ethoxylate trimethacrylate, trimethylolpropane ethoxytrimethacrylate, 1,6-hexanediol methacrylate, 1,4-butanediol dimethacrylate, 1, 2-ethanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-phenylene dimethacrylate, isocyanurate trimethacrylate, tripropylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate It may contain modifier-derived functional groups derived from one or more modifiers selected from the group consisting of

Also, according to an embodiment of the present invention, the modified conjugated diene-based polymer represented by Chemical Formula 1 may be free of metals and metalloids. Specific examples of metals and metalloids may be silicon, germanium, tin, etc. Specifically, the modified conjugated diene-based polymer of the present invention does not contain silicon, germanium and tin. good. Since the modified conjugated diene-based polymer does not contain metals and semimetals, it is possible to suppress gel formation, obtain a uniform polymer with high purity, and prevent contamination of the polymerization reactor due to gel formation. In addition, since the bonding force between carbon and carbon formed in the present invention is stronger than the bonding force between metals or semimetals and carbon, the degree of branching is increased when mixed with various additives and heated at high temperatures. It is possible to suppress the phenomenon of the reduction in the amount of metal, and it is not affected by the problem of heavy metals, the toxicity of organometallic substances, etc., so it has the advantage of improving the safety of the working environment.

The modified conjugated diene-based polymer according to one embodiment of the present invention has a structure represented by Chemical Formula 1, and the end of the polymer chain is modified, resulting in a low beta value through cross-linking between the chains. (β-value), which can effectively control cold flowability. In addition, the modified conjugated diene-based polymer according to one embodiment of the present invention has a Mooney viscosity increase rate of the modified polymer compared to the Mooney viscosity of the polymer before modification by introducing a branched structure through the modification step. can be greatly improved, resulting in improved processability when blended into a rubber composition and improved compounding properties such as tensile and viscoelastic properties.

In addition, the conjugated diene-based polymer according to one embodiment of the present invention has a molecular weight distribution (PDI; Polydispersity), which is the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), of 1.0. 05 to 5.0, specifically 2.0 to 3.5 or less, more specifically 2.5 to 3.5, having a broad molecular weight distribution. When it has a wide molecular weight distribution, it has excellent processing properties and viscoelastic properties when applied to a rubber composition.

Here, said molecular weight distribution may be calculated from the ratio (Mw/Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) as previously mentioned, wherein said number average molecular weight (Mn) is It is the common average of individual polymer molecular weights calculated by measuring the molecular weights of n polymer molecules, obtaining the total of these molecular weights, and dividing them into n, and the weight average molecular weight (Mw) is the polymer 1 shows the molecular weight distribution of the composition.

Further, the conjugated diene-based polymer according to one embodiment of the present invention satisfies the molecular weight distribution conditions and has a weight average molecular weight (Mw) of 300,000 g/mol to 1,500,000 g/mol. may be from 700,000 g/mol to 1,100,000 g/mol. Further, the conjugated diene-based polymer according to one embodiment of the present invention has a number average molecular weight (Mn) of 100,000 g/mol to 700,000 g/mol, specifically 150,000 g/mol to 500, 000 g/mol. Within this range, when applied to a rubber composition, it has excellent tensile properties, excellent processability, and kneading is easy due to improved workability of the rubber composition, so that the rubber composition has an excellent effect on the mechanical properties and the balance of physical properties. .

More specifically, the conjugated diene-based polymer according to one embodiment of the present invention is applied to a rubber composition when simultaneously satisfying the conditions of weight average molecular weight (Mw) and number average molecular weight (Mn) as well as the molecular weight distribution. It is excellent in tensile properties, viscoelasticity and processability for rubber compositions at times, and has an excellent effect in the balance of physical properties among them.

In addition, the conjugated diene-based polymer has a Mooney viscosity (MV) of 10 to 90, specifically 30 to 80, more specifically 30 to 60 at 100° C. before modification. you can Also, the modified polymer may have a mooney viscosity (MV) at 100° C. of 50 to 130, specifically 60 to 120, more specifically 65 to 120 or 70 to 110.

In the present invention, the Mooney viscosity may be measured using a Mooney viscometer, for example, Monsanto MV2000E, at 100° C., Rotor Speed 2±0.02 rpm, Large Rotor. After leaving the sample used at this time at room temperature (23±3° C.) for 30 minutes or more, 27±3 g of the sample may be collected and placed in the die cavity, and the platen may be operated for measurement.

In addition, the modified conjugated diene polymer according to one embodiment of the present invention has a Mooney viscosity increase rate of the conjugated diene polymer after modification based on the Mooney viscosity of the conjugated diene polymer before modification (hereinafter referred to as Mooney viscosity The increase rate) may be 20% or more, and from the aspect of efficiently controlling cold flow properties to greatly improve workability, it is preferably 35% or more, more preferably 50% to 150%. It's okay. Here, the increase rate of the Mooney viscosity is the difference between the Mooney viscosity of the conjugated diene-based polymer after modification and the Mooney viscosity of the conjugated diene-based polymer before modification, with the Mooney viscosity of the conjugated diene-based polymer before modification. It is a value obtained by dividing the value as a percentage, and can be calculated from Equation 1 below.

The higher the rate of increase in Mooney viscosity, the greater the increase in Mooney viscosity after modification. When the rate of increase is within the above range, the reduction in cold flowability, processability, and compounding properties due to the adjustment of the degree of branching. can be improved to an excellent standard.

In addition, the modified conjugated diene-based polymer according to one embodiment of the present invention may have a beta value (β-value) of 0.21 or less, preferably 0.10 in terms of lower cold flowability. to 0.21, or 0.10 to 0.20 or less. When the above ranges are satisfied, the cold flow control of the polymer can be greatly improved. Here, the beta value is a function of frequency and indicates the degree of branching of the polymer. A smaller value indicates an increased degree of branching, and a larger value indicates a decreased degree of branching. Specifically, the beta value is measured using a D-RPA 3000 (rubber process analyzer) manufactured by Montetech, with a frequency sweep range of 0 to 100 Hz and static strain. 3%, dynamic strain 0.25%, tan δ is measured at a measurement temperature of 100 ° C. d (log (tan δ)) / d (log (freq)) slope is taken as beta value (β-value) Indicated. Here, tan δ is a value indicated by the ratio of the viscosus modulus (G'') to the elastic modulus (G') as an index indicating general viscoelastic properties.

When the modified conjugated diene-based polymer according to one embodiment of the present invention satisfies the aforementioned molecular weight distribution, weight average molecular weight and number average molecular weight conditions, and simultaneously satisfies the beta value and Mooney viscosity range before and after modification, when applied to a rubber composition. It is possible to enjoy a well-balanced physical property improvement effect without being biased to any one of compounding properties such as tensile properties and viscoelastic properties for rubber compositions, processability, and cold flow properties.

In addition, in the modified conjugated diene-based polymer according to one embodiment of the present invention, the conjugated diene-based polymer may be a butadiene homopolymer such as polybutadiene, or a butadiene copolymer such as butadiene-isoprene copolymer. It may be a polymer.

As a specific example, the conjugated diene-based polymer contains 80 to 100% by weight of repeating units derived from a 1,3-butadiene monomer, and optionally other copolymerizable with 1,3-butadiene. The repeating unit derived from the conjugated diene-based monomer may be contained in an amount of 20% by weight or less, and within the above range, there is an effect that the 1,4-cis bond content in the polymer is not lowered. At this time, the 1,3-butadiene monomer includes 1,3-butadiene such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, or 2-ethyl-1,3-butadiene. and derivatives thereof, and other conjugated diene-based monomers copolymerizable with the 1,3-butadiene include 2-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl- 1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, etc., and any one or two or more of these compounds may be used. .

The modified conjugated diene-based polymer according to one embodiment of the present invention may be specifically a rare earth metal-catalyzed modified conjugated diene-based polymer, more specifically, a neodymium-catalyzed modified conjugated diene-based polymer. you can The neodymium-catalyzed modified conjugated diene-based polymer may be a modified conjugated diene-based polymer produced using a catalyst composition containing a neodymium compound. More specifically, the modified conjugated diene-based polymer may be a neodymium-catalyzed modified butadiene-based polymer containing repeating units derived from 1,3-butadiene monomer.

According to one embodiment of the present invention, the present invention comprises: 1) polymerizing a conjugated diene-based monomer in the presence of a catalyst composition containing a rare earth metal compound to prepare an organometallic-bonded active polymer; and 2) reacting the activated polymer with a modifier represented by Formula 2 below.

In the chemical formula 2,
A may be a hydrocarbon unit having 2 to 12 carbon atoms or a hydrocarbon unit having 2 to 12 carbon atoms containing one or more heteroatoms selected from N or O;
R _x may be hydrogen or a methyl group,
n may be an integer from 2 to 6.

Specifically, specific examples of the hydrocarbon unit and heteroatom-containing hydrocarbon unit of the modifier represented by Chemical Formula 2 of the present invention are as described above for the modified conjugated diene-based polymer, At this time, in chemical formulas 3 to 4-4, the "(meth)acrylate-derived group of chemical formula 1" may be replaced with "(meth)acrylate of chemical formula 2".

More specifically, the modifier represented by Formula 2 includes dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, and propoxylated glycerol triacrylate. , trimethylolpropane ethoxylate triacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol diacrylate, 1,2-ethanediol diacrylate, neopentyl glycol diacrylate, 1,3-butanediol diacrylate , 1,4-phenylene diacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol hydroxypentamethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, trimethylolpropane trimethacrylate, propoxylated glycerol trimethacrylate, trimethylolpropane ethoxylate trimethacrylate, trimethylolpropane ethoxytrimethacrylate, 1,6-hexanediol methacrylate, 1,4-butanediol dimethacrylate, 1,2-ethanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-phenylene dimethacrylate, isocyanurate trimethacrylate, tripropylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol It may contain one or more selected from the group consisting of dimethacrylates.

Also, according to an embodiment of the present invention, the modifier represented by Formula 2 may be free of metals and metalloids. Specific examples of metals and metalloids may be silicon, germanium, tin, etc. Specifically, the modifier of the present invention may be free of silicon, germanium and tin. Since the modifying agent does not contain metals and semimetals, it is possible to suppress gel formation during the modification reaction and obtain a uniform polymer with high purity, and it is possible to prevent contamination of the polymerization reactor due to gel formation in the polymer production process. . In addition, when the modifier contains a metal or semimetal, the bond strength between the carbon-carbon formed in the present invention is greater than the bond strength between the metal or semimetal formed with the polymer chain and carbon. Because it is stronger, it can be mixed with various additives to suppress the phenomenon of decreasing the degree of branching when heated at high temperatures. be. In addition, when the modifier contains metals and semimetals, the introduction of a branched structure is insufficient, so the physical properties required by the present invention, particularly a low beta value and a high rate of increase in Mooney viscosity, cannot be achieved. The cold flow properties of the coalesce cannot be effectively controlled and the compound properties can also be compromised.

The step 1) according to one embodiment of the present invention is a step of polymerizing a conjugated diene-based monomer in the presence of a catalyst composition containing a rare earth metal compound to prepare an active polymer, wherein the active polymer may represent an active polymer to which the organometallic is attached.

Said polymerization according to one embodiment of the invention may be carried out by coordination polymerization, by way of example in a solution polymerization process, and in batch, continuous or semi-continuous processes. good too. As a specific example, the polymerization for producing the conjugated diene-based polymer may be carried out by adding a conjugated diene-based monomer to the catalyst composition in an organic solvent and reacting it.

Specifically, when produced by solution polymerization, the conjugated diene polymer according to one embodiment of the present invention is prepared by adding a conjugated diene-based monomer to the catalyst composition in a polymerization solvent and reacting it. can be broken

As the conjugated diene-based monomer, any conjugated diene-based monomer that is commonly used in the production of a conjugated diene-based polymer can be used without any particular limitation. The conjugated diene-based monomer specifically includes 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1 ,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, or 2,4-hexadiene. Any one or a mixture of two or more may be used. More specifically, the conjugated diene-based monomer may be 1,3-butadiene.

Further, considering the physical properties of the conjugated diene-based polymer finally produced during the polymerization reaction, other monomers copolymerizable with the conjugated diene-based monomer may be further used. Specific monomers other than styrene, p-methylstyrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexylstyrene, 2,4,6 - Aromatic vinyl monomers such as trimethylstyrene and the like, and any one or a mixture of two or more thereof may be used. The other monomers may be used in an amount of 20% by weight or less based on the total weight of the monomers used in the polymerization reaction.

At this time, the conjugated diene-based monomer is not dissolved in a non-polar solvent for the entire amount used for the production of the diene-based polymer, but a part of the total amount used is dissolved in the polymerization solvent. After being polymerized, it may be dividedly added one or more times, specifically two or more times, more specifically two to four times depending on the polymerization conversion rate.

Also, the solvent that may be included during the polymerization may be a hydrocarbon-based solvent, and the hydrocarbon-based solvent may be a non-polar solvent. Specifically, the hydrocarbon solvent includes aliphatic hydrocarbon solvents such as pentane, hexane, isopentane, heptane, octane, and isooctane, and cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, and the like. or one or more selected from the group consisting of aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene, xylene, and the like. As a specific example, the hydrocarbon solvent may be an aliphatic hydrocarbon solvent such as hexane. When using the polymerization solvent, the concentration of the monomer is not particularly limited, but may be 3 to 80 wt%, more specifically, 10 to 30 wt%.

Also, during the polymerization, a molecular weight modifier such as trimethylaluminum, diisobutylaluminum hydride or trimethylsilane; a reaction terminator for completing the polymerization reaction such as polyoxyethylene glycol phosphate; or 2,6-di- Additives such as antioxidants such as t-butyl paracresol may also be used. In addition, additives such as chelating agents, dispersants, pH adjusters, oxygen scavengers or oxygen scavengers are optionally optionally added to facilitate solution polymerization. It may be used further.

Also, the polymerization reaction may be carried out at a temperature of from 20°C to 200°C, more specifically from 20°C to 100°C.

The polymerization reaction may be carried out within the above temperature range for 5 minutes to 3 hours, specifically 15 minutes to 2 hours, more specifically 30 minutes to 2 hours, until the conversion rate of the conjugated diene polymer reaches 100%. may be done.

A rare earth metal catalyst composition according to one embodiment of the present invention may comprise (a) a rare earth metal compound, (b) an alkylating agent (c) a halogen compound, wherein further comprising a conjugated diene-based monomer. can be

Specifically, the catalyst composition may be prepared by sequentially adding a rare earth metal compound, an alkylating agent, a halogen compound, and optionally a conjugated diene-based monomer into a hydrocarbon-based solvent and mixing them. .

At this time, in order to promote the generation of catalytically active species, the mixing step may be performed at a temperature range of -10°C to 30°C, and heat treatment is performed in parallel to meet the temperature conditions. may

More specifically, the catalyst composition is subjected to a first heat treatment at a temperature of -10°C to 30°C after mixing a rare earth metal compound, an alkylating agent, and a solvent, and adding a halogen compound to the resulting mixture. , a second heat treatment at a temperature range of -10°C to 30°C.

In the catalyst composition produced by the production method as described above, catalytically active species are generated due to the interaction of the constituent components. The prepared catalyst composition may further comprise a step of aging at low temperature conditions.

In addition, the hydrocarbon-based solvent in the catalyst composition may be one or more of the above-described hydrocarbon-based solvents contained during polymerization.

Further, a part of the conjugated diene-based monomer used in the polymerization reaction is premixed with the catalyst composition and used in the form of a preforming catalyst composition, thereby improving the catalytic activity. Furthermore, it has the effect of stabilizing the produced conjugated diene polymer.

Each component will be described in detail below.

(a) Rare Earth Metal Compound In the catalyst composition according to one embodiment of the present invention, the rare earth metal compound forms a catalytically active species for polymerization of a conjugated diene after being activated by an alkylating agent.

As such a rare earth metal compound, any compound that is usually used in the production of a conjugated diene polymer can be used without any particular limitation. Specifically, the rare earth metal compound may be any one or two or more compounds of rare earth metals having an atomic number of 57 to 71 such as lanthanum, neodymium, cerium, gadolinium or praseodymium, More specifically, it may be a compound containing one or more selected from the group consisting of neodymium, lanthanum and gadolinium.

In addition, the rare earth metal compound is the rare earth metal-containing carboxylate (e.g., neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate). , neodymium maleate, neodymium oxalate, neodymium 2-ethylhexanoate, neodymium neodecanoate, etc.), organic phosphates (e.g., neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate salt, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis(1-methylheptyl) phosphate, neodymium bis(2-ethylhexyl) phosphate, or neodymium didecyl phosphate), organic phosphonates (e.g., neodymium butylphosphonate, neodymium pentylphosphonate, neodymium hexylphosphonate, neodymium heptylphosphonate, neodymium octylphosphonate, neodymium (1-methylheptyl)phosphonate, neodymium (2-ethylhexyl) phosphonate, neodymium decyl phosphonate, neodymium dodecyl phosphonate or neodymium octadecyl phosphonate), organic phosphinates (e.g. neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexylphosphinate, neodymium heptylphosphinate, neodymium octylphosphinate, neodymium (1-methylheptyl)phosphinate or neodymium (2-ethylhexyl)phosphinate, etc.), carbamate (e.g. neodymium dimethylcarbamate, neodymium diethylcarbamate) salt, neodymium diisopropyl carbamate, neodymium dibutyl carbamate or neodymium dibenzyl carbamate), dithiocarbamate (e.g. neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyl dithiocarbamate or neodymium dibutyldithiocarbamine acid salts, etc.), xanthates (e.g., neodymium methyl xanthate, neodymium ethyl xanthate, neodymium isopropyl xanthate, neodymium butyl xanthate, neodymium benzyl xanthate, etc.), β-diketonates (e.g., neodymium acetyl Acetonate, neodymium trifluoroacetylacetonate, neodymium hexafluoroacetylacetonate or neodymium benzoylacetonate tonate, etc.), alkoxides or aryloxides (e.g., neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium phenoxide, neodymium nonylphenoxide, etc.), halides or pseudohalides (neodymium fluoride, neodymium chloride, neodymium bromide, neodymium iodide, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, or neodymium azide), oxyhalides (such as neodymium oxyfluoride, neodymium oxychloride, or neodymium oxybromide), or one or more rare earth metals - organic rare earth metal compounds containing carbon bonds (e.g. _Cp3Ln , _Cp2LnR ', _Cp2LnCl , _CpLnCl2 , CpLn(cyclooctatetraene), _{( C5Me5} ) _2LnR ', Ln(R' ) ₃ , Ln(allyl) ₃ , or Ln(allyl) ₂ Cl, etc., wherein Ln is a rare earth metal element and R′ is a monovalent organic group bonded to the metal atom via a carbon atom. and may be a hydrocarbyl group), and may include any one or a mixture of two or more thereof.

More specifically, the rare earth metal compound may be a neodymium compound represented by Formula 5 below:

In Chemical Formula 5, R ₁ to R ₃ are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms.

More specifically, in the rare earth metal compound, in Chemical Formula 5, R ₁ is a linear or branched alkyl group having 6 to 12 carbon atoms, and R ₂ and R ₃ are each independently hydrogen. or a linear or branched alkyl group having 2 to 6 carbon atoms, provided that R ₂ and R ₃ are not both hydrogen atoms, and may be a neodymium compound, more particularly , wherein R ₁ is a linear or branched alkyl group having 6 to 8 carbon atoms, and R ₂ and R ₃ each independently represent a linear or branched chain having 2 to 6 carbon atoms. It may be a neodymium compound that is a branched alkyl group.

As described above, when the neodymium compound of Formula 5 includes a carboxylate ligand having alkyl groups of various lengths and having 2 or more carbon atoms at the a position, steric changes occur around the central neodymium metal. It can induce and block the aggregation phenomenon between compounds, resulting in high conversion to active species due to suppression of oligomerization. Such a neodymium compound has a high solubility in a polymerization solvent, and the ratio of neodymium located in the central portion, which is difficult to convert to a catalytically active species, is reduced, thereby increasing the conversion rate to a catalytically active species.

More specifically, the rare earth metal compound is Nd(2,2-diethyldecanoate) ₃ , Nd(2,2-dipropyldecanoate) ₃ , Nd(2,2-dibutyldecanoate) ₃ , Nd(2,2-dihexyldecanoate) ₃ , Nd(2,2-dioctyldecanoate) ₃ , Nd(2-ethyl-2-propyldecanoate) ₃ , Nd(2-ethyl-2- butyl decanoate) ₃ , Nd(2-ethyl-2-hexyl decanoate) ₃ , Nd(2-propyl-2-butyl decanoate) ₃ , Nd(2-propyl-2-hexyl decanoate) ₃ , Nd(2-propyl-2-isopropyldecanoate) ₃ , Nd(2-butyl-2-hexyldecanoate) _{3 , Nd(2-hexyl-2-octyldecanoate) 3 ,} Nd(2 ,2-diethyloctanoate) ₃ , Nd(2,2-dipropyloctanoate) _{3 , Nd(2,2-dibutyloctanoate) 3 ,} Nd(2,2-dihexyloctanoate) ₃ , Nd(2-ethyl-2-propyloctanoate) ₃ , Nd(2-ethyl-2-hexyloctanoate) ₃ , Nd(2,2-diethyl nonanoate) ₃ , Nd(2,2-dipropyl nonanoate) ₃ , Nd(2,2-dibutyl nonanoate) ₃ , Nd(2,2-dihexyl nonanoate) ₃ , Nd(2-ethyl-2-propyl nonanoate) ₃ and Nd(2-ethyl-2 -hexyl nonanoate) ₃ or a mixture of two or more selected from the group consisting of 3. In addition, when considering excellent solubility in a polymerization solvent without fear of oligomerization, a conversion rate to catalytically active species, and an excellent effect of improving catalytic activity thereby, the neodymium compound is Nd(2,2-diethyldeca noate) ₃ , Nd(2,2-dipropyldecanoate) ₃ , Nd(2,2-dibutyldecanoate) ₃ , Nd(2,2-dihexyldecanoate) ₃ , and Nd(2,2-dipropyldecanoate) 3 . 2-dioctyl decanoate) ₃ , or a mixture of two or more selected from the group consisting of 3.

Also, the rare earth metal compound may have a solubility of about 4 g or more per 6 g of the non-polar solvent at room temperature (23±5° C.). In the present invention, the solubility of a neodymium compound means the degree of clear dissolution without turbidity. By exhibiting such high solubility, excellent catalytic activity can be exhibited.

For example, the rare earth metal compound may be used in a content of 0.1 to 0.5 mmol, more specifically 0.1 to 0.2 mmol, per 100 g of the conjugated diene-based monomer used for polymerization, Within this range, the catalyst activity is high and the concentration of the catalyst is appropriate, so there is no need for a separate recovery process.

The rare earth metal compound may be used, for example, in the form of a reactant with a Lewis base. This reactant has the effect of improving the solubility of the rare earth metal compound in the solvent and allowing it to be stored in a stable state for a long period of time due to the Lewis base. For example, the Lewis base may be used in a ratio of 30 mol or less, or from 1 to 10 mol, per 1 mol of the rare earth element. Examples of the Lewis base include acetylacetone, tetrahydrofuran, pyridine, N,N-dimethylformamide, thiophene, diphenyl ether, triethylamine, organic phosphorus compounds, monovalent or divalent alcohols, and the like.

(b) Alkylating agent In the catalyst composition for conjugated diene polymerization according to one embodiment of the present invention, the alkylating agent is an organometallic compound capable of transferring a hydrocarbyl group to another metal and serves as a co-catalyst. do. The alkylating agent can be used without particular limitation as long as it is usually used as an alkylating agent in the production of diene-based polymers.

Specifically, the alkylating agent is soluble in a non-polar solvent, specifically a non-polar hydrocarbon solvent, and is capable of may be an organometallic compound or a boron-containing compound comprising More specifically, the alkylating agent may be one or a mixture of two or more selected from the group consisting of organoaluminum compounds, organomagnesium compounds and organolithium compounds.

In the alkylating agent, the organoaluminum compound may be specifically a compound of Formula 6 below:
[Chemical Formula 6]
Al(R) _z (X) _3-z
In the chemical formula 6,
Each R is independently a monovalent organic group bonded to an aluminum atom via a carbon atom, and is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a cycloalkyl group having 2 to 2 carbon atoms. 20 alkenyl group, cycloalkenyl group having 3 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, arylalkyl group having 7 to 20 carbon atoms, alkylaryl group having 7 to 20 carbon atoms, aryl group, or 2 carbon atoms hydrocarbyl groups such as alkynyl groups from to 32; or heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms, boron atoms, silicon atoms, sulfur atoms, and yne atoms replacing carbons in the hydrocarbyl group structure. may be a heterohydrocarbyl group containing at least one
each X is independently selected from the group consisting of a hydrogen atom, a halogen group, a carboxyl group, an alkoxy group, and an aryloxy group;

More specifically, the organoaluminum compound is diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride (DIBAH), di-n-octylaluminum hydride, Diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride, phenylisobutylaluminum hydride, phenyl- n-octyl aluminum hydride, p-tolylethyl aluminum hydride, p-tolyl-n-propyl aluminum hydride, p-tolyl isopropyl aluminum hydride, p-tolyl-n-butyl aluminum hydride, p-tolyl isobutyl aluminum hydride, p-tolyl - dihydrocarbyl aluminum hydride such as n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, benzyl-n-butylaluminum hydride, benzylisobutylaluminum hydride or benzyl-n-octylaluminum hydride hydride; hydrocarbyl aluminum dihydride such as ethyl aluminum dihydride, n-propyl aluminum dihydride, isopropyl aluminum dihydride, n-butyl aluminum dihydride, isobutyl aluminum dihydride or n-octyl aluminum dihydride; Preferably diisobutylaluminum hydride may be included.

Alternatively, the organoaluminum compound may be an aluminoxane.

The aluminoxane may be prepared by reacting a trihydrocarbylaluminum-based compound with water, specifically, it may be a linear aluminoxane represented by Formula 7a below or a cyclic aluminoxane represented by Formula 7b below:

In Formulas 7a and 7b above, R is a monovalent organic group bonded to an aluminum atom through a carbon atom and is the same as R defined above, and x and y are each independently 1 or more. , specifically an integer from 1 to 100, more specifically from 2 to 50.

More specifically, the aluminoxane includes methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, butylaluminoxane, isobutylaluminoxane, n-pentylaluminoxane, neopentylaluminoxane, n- hexylaluminoxane, n-octylaluminoxane, 2-ethylhexylaluminoxane, cyclohexylaluminoxane, 1-methylcyclopentylaluminoxane, phenylaluminoxane, 2,6-dimethylphenylaluminoxane, etc., any one or two or more of these Mixtures may be used.

Further, in the aluminoxane compound, the modified methylaluminoxane is obtained by substituting the methyl group of methylaluminoxane with a modifying group (R), specifically, a hydrocarbon group having 2 to 20 carbon atoms. 8 may be a compound of:

In Formula 8, R is as defined above, and m and n may each be an integer of 2 or more. In Formula 8, Me means a methyl group.

More specifically, in Chemical Formula 8, R is a linear or branched alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, carbon a cycloalkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an aryl group, or an alkynyl group having 2 to 20 carbon atoms more specifically, a linear or branched alkyl group having 2 to 10 carbon atoms such as an ethyl group, an isobutyl group, a hexyl group or an octyl group, and more specifically , an isobutyl group.

More specifically, the modified methylaluminoxane may be one in which about 50 mol % to 90 mol % of the methyl groups of methylaluminoxane are substituted with the hydrocarbon groups. When the content of substituted hydrocarbon groups in the modified methylaluminoxane is within the above range, alkylation can be promoted and catalytic activity can be increased.

Such a modified methylaluminoxane may be produced by a conventional method, and specifically, may be produced using trimethylaluminum and an alkylaluminum other than trimethylaluminum. At this time, the alkylaluminum may be triisobutylaluminum, triethylaluminum, trihexylaluminum, trioctylaluminum, or the like, and any one or a mixture of two or more thereof may be used.

On the other hand, the organomagnesium compound as the alkylating agent is a magnesium compound that contains at least one magnesium-carbon bond and is soluble in a nonpolar solvent, specifically, a nonpolar hydrocarbon solvent. Specifically, the organomagnesium compound may be a compound of Formula 8a:
[Chemical Formula 9a]
Mg(R) ₂
In Formula 9a, each R is independently a monovalent organic group and is the same as R defined above.

More specifically, the organomagnesium compound of Formula 9a includes alkylmagnesium compounds such as diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, diphenylmagnesium, or dibenzylmagnesium. .

Alternatively, the organomagnesium compound may be a compound of Formula 9b below:
[Chemical Formula 9b]
RMgX
In Formula 9b, R is a monovalent organic group that is the same as R defined above, and X is selected from the group consisting of a hydrogen atom, a halogen group, a carboxyl group, an alkoxy group and an aryloxy group. It is what is done.

More specifically, the organomagnesium compound of Formula 9b includes hydrocarbylmagnesium hydrides such as methylmagnesium hydride, ethylmagnesium hydride, butylmagnesium hydride, hexylmagnesium hydride, phenylmagnesium hydride, and benzylmagnesium hydride. , methylmagnesium chloride, ethylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, phenylmagnesium chloride, benzylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, butylmagnesium bromide, hexylmagnesium bromide, phenylmagnesium bromide , hydrocarbyl magnesium halides such as benzylmagnesium bromide, and hydrocarbyl magnesium halides such as methylmagnesiumhexanoate, ethylmagnesiumhexanoate, butylmagnesiumhexanoate, hexylmagnesiumhexanoate, phenylmagnesiumhexanoate, benzylmagnesiumhexanoate, etc. Magnesium carboxylate and hydrocarbyl magnesium alkoxide such as methylmagnesium ethoxide, ethylmagnesium ethoxide, butylmagnesium ethoxide, hexylmagnesium ethoxide, phenylmagnesium ethoxide, benzylmagnesium ethoxide, or methylmagnesiumphenoxide, ethylmagnesiumphenoxide , butyl magnesium phenoxide, hexyl magnesium phenoxide, phenyl magnesium phenoxide, hydrocarbyl magnesium aryloxides such as benzyl magnesium phenoxide, and the like.

In addition, as the alkylating agent, the organolithium compound is R'-Li alkyllithium (at this time, R' is a linear or branched alkyl group having 1 to 20 carbon atoms, more specifically is a linear alkyl group having 1 to 8 carbon atoms) may be used. More specific examples include methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, isobutyllithium, pentyllithium, isopentyllithium and the like. A mixture of one or more may be used.

Among the above compounds, the alkylating agent that can be used in the present invention may specifically be diisobutylaluminum hydride (DIBAH), which can act as a molecular weight modifier during polymerization.

In addition, the alkylating agent is a modified methyl ester in that the catalyst activity and reactivity can be further improved by using an aliphatic hydrocarbon-based single-phase solvent as the solvent system used in the production of the catalyst composition. It may be an aluminoxane.

(c) Halogen compound In the catalyst composition for conjugated diene polymerization according to one embodiment of the present invention, the halogen compound is not particularly limited in kind, but is usually used as a halogenating agent during the production of a diene polymer. It can be used without any special restrictions.

Specifically, the halogen compound includes a simple substance of halogen, an interhalogen compound, a hydrogen halide, an organic halide, a non-metal halide, a metal halide, or an organic metal halide. Any one or a mixture of two or more may be used. Among these, when considering the effect of improving the catalytic activity and the resulting excellent reactivity improvement, the halogen compound may be any one or two selected from the group consisting of organic halides, metal halides and organometallic halides. Mixtures of the above may be used.

More specifically, the halogen element includes fluorine, chlorine, bromine, and iodine.

Further, the interhalogen compound specifically includes iodomonochloride, iodomonobromide, iodotrichloride, iodopentafluoride, iodomonofluoride, iodotrifluoride, and the like.

Further, the hydrogen halide specifically includes hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide.

Further, as the organic halide, specifically, t-butyl chloride (t-BuCl), t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-di-phenylmethane, bromo-di-phenyl Methane, triphenylmethyl chloride, triphenylmethyl bromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane (TMSCl), benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, methyl chloroformate, methyl bromoformate, iodomethane, diiodomethane, triiodomethane (also called "iodoform"), tetraiodomethane, 1-iodopropane, 2-iodopropane, 1,3-diiodopropane, t -butyl iodide, 2,2-dimethyl-1-iodopropane (also called "neopentyl iodide"), allyl iodide, iodobenzene, benzyl iodide, diphenylmethyl iodide, triphenylmethyl iodide, benzylidene iodide ("benzal iodide ), trimethylsilyl iodide, triethylsilyl iodide, triphenylsilyl iodide, dimethyldiiodosilane, diethyldiiodosilane, diphenyldiiodosilane, methyltriiodosilane, ethyltriiodosilane, phenyltriiodosilane, benzoyl iodide, propionyl iodide, methyl iodoformate and the like.

Further, as the non-metal halide, specifically, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, boron trifluoride, boron trichloride, boron tribromide, tetrafluoride silicon chloride, silicon tetrachloride ( _SiCl4 ), silicon tetrabromide, arsenic trichloride, arsenic tribromide, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide, silicon tetraiodide, triiodine arsenic, tellurium tetraiodide, boron triiodide, phosphorus triiodide, phosphorus oxyiodide, selenium tetraiodide, and the like.

The metal halides specifically include tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, antimony tribromide, aluminum trifluoride, and gallium trichloride. , gallium tribromide, gallium trifluoride, indium trichloride, indium tribromide, indium trifluoride, titanium tetrachloride, titanium tetrabromide, zinc dichloride, zinc dibromide, zinc difluoride, triiodine Aluminum oxide, gallium triiodide, indium triiodide, titanium tetraiodide, zinc diiodide, germanium tetraiodide, tin tetraiodide, tin diiodide, antimony triiodide, magnesium diiodide, etc. be done.

Further, as the organometallic halide, specifically, dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide , ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride (EASC), isobutylaluminum sesquichloride, methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium bromide, n-butylmagnesium chloride, n-butylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium chloride, trimethyltin chloride, trimethyltin bromide, triethyltin chloride, triethyltin bromide, di-t-butyltin dichloride, di-t -butyltin dibromide, di-n-butyltin dichloride, di-n-butyltin dibromide, tri-n-butyltin chloride, tri-n-butyltin bromide, methylmagnesium iodide, dimethylaluminum iodide, diethylaluminum iodide, di - n-butylaluminum iodide, diisobutylaluminum iodide, di-n-octylaluminum iodide, methylaluminum diiodide, ethylaluminum diiodide, n-butylaluminum diiodide, isobutylaluminum diiodide, methylaluminum sesquiodide, ethylaluminum sesquiodide, isobutylaluminum sesquiodide, ethylmagnesium iodide, n-butylmagnesium iodide, isobutylmagnesium iodide, phenylmagnesium iodide, benzylmagnesium iodide, trimethyltin iodide, triethyltin iodide, tri -n-butyltin diiodide, di-n-butyltin diiodide, di-t-butyltin diiodide and the like.

Further, the catalyst composition for producing a conjugated diene polymer according to one embodiment of the present invention comprises a non-coordinating anion-containing compound or a non-coordinating anion precursor compound instead of or together with the halogen compound. may include

Specifically, in the compound containing the non-coordinating anion, the non-coordinating anion is an anion with a large steric volume that does not form a coordinate bond with the active center of the catalyst system due to steric hindrance. may be a tetraarylborate anion, a fluorinated tetraarylborate anion, or the like. In addition, the compound containing the non-coordinating anion may contain a carbonium cation such as a triarylcarbonium cation; an ammonium cation such as an N,N-dialkylanilinium cation; It may contain a cation or a counter cation such as a phosphonium cation. More specifically, the compound containing the non-coordinating anion is triphenylcarboniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarboniumtetrakis [ 3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, or the like.

The non-coordinating anion precursor is a compound capable of forming a non-coordinating anion under the reaction conditions, and is a triarylboron compound (BE ₃ , where R is a pentafluorophenyl group or a strongly electron-withdrawing aryl group such as a 3,5-bis(trifluoromethyl)phenyl group).

The solvent according to one embodiment of the present invention may specifically be a non-polar solvent that is not reactive with the catalyst components. Specifically, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, cyclopentane, cyclohexane, methyl linear, branched or cyclic aliphatic hydrocarbons having 5 to 20 carbon atoms, such as cyclopentane or methylcyclohexane; petroleum ether or petroleum spirits, or kerosene, etc. or an aromatic hydrocarbon solvent such as benzene, toluene, ethylbenzene, xylene, etc., any one or two of these Mixtures of the above may be used. More specifically, the non-polar solvent may be the linear, branched or cyclic aliphatic hydrocarbon having 5 to 20 carbon atoms or a mixed solvent of the aliphatic hydrocarbon, and more specifically, It may be n-hexane, cyclohexane, or mixtures thereof.

Also, the reaction solvent may be appropriately selected according to the constituents of the catalyst composition, particularly the type of alkylating agent.

Specifically, in the case of an alkylaluminoxane such as methylaluminoxane (MAO) or ethylaluminoxane as the alkylating agent, it is not easily dissolved in an aliphatic hydrocarbon solvent, so an aromatic hydrocarbon solvent may be appropriately used. .

In addition, when modified methylaluminoxane is used as the alkylating agent, an aliphatic hydrocarbon solvent may be appropriately used. In this case, it is possible to realize a single solvent system together with an aliphatic hydrocarbon solvent such as hexane, which is mainly used as a polymerization solvent, which is more advantageous for the polymerization reaction. In addition, the aliphatic hydrocarbon-based solvent can promote catalytic activity, and the catalytic activity can further improve reactivity.

The components within the catalyst composition as described above form catalytically active species through interactions with each other. Accordingly, the catalyst composition according to one embodiment of the present invention has an optimum content of the components so as to exhibit higher catalytic activity and excellent polymerization reactivity during the polymerization reaction for forming the conjugated diene-based polymer. may be included in combination with

Specifically, the catalyst composition may comprise 1 mol to 100 mol, specifically 3 to 20 mol, of the alkylating agent per 1 mol of the rare earth metal compound. The catalyst composition may contain 1 to 20 mol of the halogen compound, specifically 1 to 5 mol, more specifically 1 to 3 mol, per 1 mol of the rare earth metal compound. OK. By containing the alkylating agent and the halogen compound within the above ranges, the catalytic reaction can be easily controlled, and side reactions can be efficiently suppressed.

In addition, the catalyst composition may further include a solvent in an amount of 20 to 20,000 mol, more specifically 100 to 1,000 mol, per 1 mol of the rare earth metal compound.

In the method for preparing a conjugated diene polymerization catalyst according to an embodiment of the present invention, step S2 is a step of preforming by adding a conjugated diene-based monomer to the catalyst composition. When the prepolymerization is carried out in this manner, not only can the catalytic activity be improved, but also the conjugated diene-based polymer to be produced can be more stabilized. Concretely, as the conjugated diene-based monomer, any conjugated diene-based monomer that is usually used for the production of a conjugated diene-based polymer can be used without any particular limitation. Specifically, the conjugated diene-based monomers include 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1 ,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, or 2,4-hexadiene, and any of these one or a mixture of two or more may be used.

In addition, the conjugated diene-based monomer that can be used in the preparation of the catalyst may be used in a part of the total amount of monomers used in the polymerization. 1 to 100 mol, more specifically 1 to 50 mol, and even more specifically 20 to 40 mol may be used per 1 mol of the metal compound.

The active polymer prepared in step 1) according to an embodiment of the present invention may specifically be a rare earth metal-catalyzed conjugated diene-based polymer, more specifically a neodymium-catalyzed conjugated diene-based polymer. can be The neodymium-catalyzed conjugated diene-based polymer may represent a conjugated diene-based polymer that includes organometallic moieties that are derived from, i.e., catalyst-activated, catalyst compositions that include a neodymium compound. More specifically, the conjugated diene-based polymer may be a neodymium-catalyzed butadiene-based polymer containing repeating units derived from 1,3-butadiene monomer.

In the present invention, the activated organometallic site of the conjugated diene polymer means an activated organometallic site at the end of the conjugated diene polymer (activated organometallic site at the end of the molecular chain), may be activated organometallic moieties in the chain or activated organometallic moieties in the side chains, among which the activated organic moieties of the conjugated diene-based polymer by anionic polymerization or coordinative anionic polymerization; When providing metal moieties, the activated organometallic moieties may be terminal activated organometallic moieties.

The step 2) according to one embodiment of the present invention is a step of reacting the activated polymer with a modifier represented by Formula 2 to form a modified conjugated diene-based polymer.

The modification step may be carried out by a conventional modification method other than using the conjugated diene-based polymer of the present invention. Specifically, the step 2) is performed by adding the modifier represented by the chemical formula 2 to the mixture produced in the polymerization step and mixing for a certain period of time. The modification step may be performed using a batch reactor, or may be performed using equipment such as a multi-stage continuous reactor or an in-line mixer. The modification step may preferably be carried out at the same temperature and pressure conditions as the polymerization step. Specifically, it may be performed at a temperature of 20°C to 200°C.

In addition, the modifier according to one embodiment of the present invention may be reacted by adding 0.1 to 20 parts by weight based on 100 parts by weight of the conjugated diene monomer, specifically 0.1 to 20 parts by weight. 1 to 10 parts by weight, more specifically 0.1 to 3 parts by weight may be added for reaction.

After the modification step, additives such as a reaction terminator such as polyoxyethylene glycol phosphate; or an antioxidant such as 2,6-di-t-butyl paracresol are added to terminate the overall reaction. It may be used further. In addition, additives such as chelating agents, dispersants, pH adjusters, oxygen scavengers or oxygen scavengers are optionally optionally added to facilitate solution polymerization. Further may be used. Thereafter, a desolvation treatment such as steam stripping to lower the partial pressure of the solvent through the supply of water vapor, or a vacuum drying process may optionally be further performed. In addition, precipitation and filtration, drying, separation steps, etc. may be further performed to obtain the polymer.

Furthermore, the present invention provides a rubber composition containing the conjugated diene-based polymer and a molded article produced from the rubber composition.

The rubber composition according to one embodiment of the present invention contains a conjugated diene polymer in an amount of 0.1% by weight or more and 100% by weight or less, specifically 10% by weight to 100% by weight, more specifically 20% by weight. to 90% by weight. If the content of the conjugated diene-based polymer is less than 0.1% by weight, as a result, the abrasion resistance and crack resistance of molded articles, such as tires, produced using the rubber composition are improved. The improvement effect may be insignificant.

In addition, the rubber composition may further contain other rubber components as necessary in addition to the modified conjugated diene-based polymer. At this time, the rubber component accounts for 90% by weight of the total weight of the rubber composition It may be included in the following amounts. Specifically, it may be contained in an amount of 1 to 900 parts by weight with respect to 100 parts by weight of the modified conjugated diene copolymer.

The rubber component may be natural rubber or synthetic rubber, for example, natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubber such as modified natural rubber (ENR), deproteinized natural rubber (DPNR), hydrogenated natural rubber; styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR) , ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co- isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicon rubber, epichlorohydrin rubber, halogenated butyl rubber, etc. Any one or a mixture of two or more of these may be used.

In addition, the rubber composition may contain a filler of 0.1 to 150 parts by weight with respect to 100 parts by weight of the conjugated diene polymer, and the filler may be silica-based, carbon black or A combination of these may be used. Specifically, the filler may be carbon black.

The carbon black-based filler is not particularly limited, but for example, has a nitrogen adsorption specific surface area (N ₂ SA, measured according to JIS K 6217-2:2001) of 20 m ² /g to 250 m ² /g. g. Further, the carbon black may have a dibutyl phthalate oil absorption (DBP) of 80 cc/100 g to 200 cc/100 g. If the nitrogen adsorption specific surface area of the carbon black exceeds ²⁵⁰ m ² /g, the processability of the rubber composition may deteriorate. . Also, if the DBP oil absorption of the carbon black exceeds 200 cc/100 g, the processability of the rubber composition may be deteriorated, and if it is less than 80 cc/100 g, the reinforcing performance of the carbon black may be insignificant.

The silica is not particularly limited, but may be, for example, wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, colloidal silica, or the like. Specifically, the silica may be wet silica, which has the most significant effect of improving fracture properties and wet grip. In addition, the silica has a nitrogen adsorption specific surface area (nitrogen surface area per gram, N ₂ SA) of 120 m ² /g to 180 m ² /g, and a CTAB (cetyl trimethylammonium bromide) adsorption specific surface area of 100 m ² /g to It may be 200 m ² /g. If the nitrogen adsorption specific surface area of the silica is less than 120 m ² /g, the reinforcing performance of the silica may deteriorate, and if it exceeds 180 m ² /g, the processability of the rubber composition may deteriorate. Further, if the CTAB adsorption specific surface area of the silica is less than 100 m ² /g, there is a risk that the reinforcing performance of silica as a filler will decrease, and if it exceeds 200 m ² /g, the processability of the rubber composition will be impaired. There is a risk that it will decrease.

On the other hand, when silica is used as the filler, a silane coupling agent may be used together to improve reinforcement and low heat build-up.

Specific examples of the silane coupling agent include bis(3-triethoxysilylpropyl) tetrasulfide, bis(3-triethoxysilylpropyl) trisulfide, bis(3-triethoxysilylpropyl) disulfide, bis(2 -triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2 -mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2 -triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, or dimethoxymethylsilyl propylbenzothiazolyl tetrasulfide, etc., and any one or a mixture of two or more of these may be used. More specifically, when considering the effect of improving reinforcing properties, the silane coupling agent may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

Also, the rubber composition according to one embodiment according to the present invention may be sulfur temporarily bridgeable, thereby further comprising a vulcanizing agent.

The vulcanizing agent may specifically be sulfur powder, and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. When contained within the above range, the vulcanized rubber composition can ensure the necessary elastic modulus and strength, and at the same time, can obtain low fuel consumption.

In addition to the above components, the rubber composition according to one embodiment of the present invention contains various additives commonly used in the rubber industry, specifically vulcanization accelerators, process oils, plasticizers, anti-aging agents, Anti-scorch agents, zinc white, stearic acid, thermosetting or thermoplastic resins, or the like may further be included.

The vulcanization accelerator is not particularly limited, and specifically includes M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfen Thiazole compounds such as amide) or guanidine compounds such as DPG (diphenylguanidine) may be used. The vulcanization accelerator may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

Further, the process oil acts as a softening agent in the rubber composition, and may specifically be a paraffinic, naphthenic or aromatic compound, more specifically a tensile Aromatic process oils may be used for strength and antiwear considerations, and naphthenic or paraffinic process oils for hysteresis loss and low temperature properties considerations. The process oil may be contained in a content of 100 parts by weight or less with respect to 100 parts by weight of the rubber component, and when contained in the above content, the tensile strength and low heat buildup (fuel efficiency) of the vulcanized rubber are reduced. can be prevented.

Further, as the anti-aging agent, specifically, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6- Examples include ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, and high-temperature condensates of diphenylamine and acetone. The antioxidant may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

The rubber composition according to one embodiment of the present invention can be obtained by kneading using a kneader such as a Banbury mixer, a roll, an internal mixer, etc. according to the above formulation, and has a low heat generation due to a vulcanization step after molding. It is possible to obtain a rubber composition having excellent properties and abrasion resistance.

As a result, the rubber composition can be used in various tire components such as tire tread, undertread, sidewall, cauldron coating rubber, belt coating rubber, bead filler, chafer, or bead coating rubber, anti-vibration rubber, belt conveyor, hose, etc. It is useful for manufacturing various industrial rubber products.

Molded articles manufactured using the rubber composition may include tires or tire treads.

The present invention will be described in more detail below by way of examples. However, the following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

[Example]
[Example 1]
Under nitrogen conditions, a 10 L reactor was charged with 2.7 kg of hexane and 300 g of 1,3-butadiene and heated to 70.degree. Here, a hexane solution of 0.38 mmol neodymium versatate (NdV), 3.7 mmol diisobutylaluminum hydride (DIBAH), 0.96 mmol diethylaluminum chloride, 1,3-butadiene 13. After adding the catalyst composition prepared by reacting with 2 mmol, polymerization was allowed to proceed for 60 minutes. The conversion of 1,3-butadiene to polybutadiene was approximately 100%. After the polymerization reaction of 1,3-butadiene was completed, a hexane solution containing 1.5 g (7.6 mmol) of 1,4-butanediol diacrylate as a modifier was added to the polymerization solution and then heated to 70°C. for 30 minutes. A hexane solution containing 0.5 g of polyoxyethylene glycol phosphate as a polymerization terminator and a hexane solution containing 0.5 g of 2,6-di-t-butyl-p-cresol as an antioxidant were added. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then hot roll dried to remove the remaining solvent and water to produce a modified conjugated diene polymer.

[Example 2]
In Example 1, the modified conjugated diene polymer was prepared in the same manner as in Example 1, except that a hexane solution containing 2.4 g of 1,4-butanediol diacrylate was used as a modifier. manufactured.

[Example 3]
Modified conjugated diene polymerization was carried out in the same manner as in Example 1, except that a hexane solution containing 4.74 g (13.5 mmol) of pentaerythritol tetraacrylate was used as a modifier. produced a coalescence.

[Example 4]
In Example 1, the modified conjugated diene was prepared in the same manner as in Example 1, except that a hexane solution containing 4.0 g (13.5 mmol) of trimethylolpropane triacrylate was used as a modifier. A polymer was produced.

[Comparative Example 1]
An unmodified conjugated diene polymer was prepared in the same manner as in Example 1, except that the mixture was stirred at 70° C. for 30 minutes without using a modifier.

[Comparative Example 2]
Modified conjugated diene polymerization was carried out in the same manner as in Example 1, except that a hexane solution containing 1.7 g (13.5 mmol) of n-butyl acrylate was used as a modifier. produced a coalescence.

[Comparative Example 3]
A modified conjugated diene polymer was prepared in the same manner as in Example 1 except that a hexane solution containing 3.4 g (27 mmol) of n-butyl acrylate was used as a modifier. manufactured.

[Comparative Example 4]
A modified conjugated diene polymer was prepared in the same manner as in Example 1, except that a hexane solution containing 2.9 g (7.6 mmol) of dibutyltin diacrylate was used as a modifier. manufactured.

At this time, dibutyltin diacrylate was prepared by placing a mixture of dibutyltin oxide (7.5 g, 30 mmol) and acrylic acid (4.3 g, 60 mmol) in a mixed solvent of 300 ml of toluene and 200 ml of acetonitrile, and heating at 80° C. for 5 hours. After stirring at , the mixed solution was concentrated to 1/4, the temperature was lowered to 0° C., and left for 48 hours to recrystallize. (8.0 g, 21.3 mmol, yield: 71%)
<Experimental example 1>
Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (PDI), Mooney viscosity (MV), and beta value of each polymer prepared in Examples and Comparative Examples were measured by the following methods. (β-value) were measured respectively.

1) weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (PDI)
After dissolving each polymer in tetrahydrofuran (THF) for 30 minutes at 40 ° C., each molecular weight was measured by loading and flowing gel permeation chromatography (GPC: gel permeation chromatography), weight average molecular weight and number average The molecular weight distribution was calculated from the molecular weight ratio. At this time, two PLgel Olexis columns (trade name, Polymer Laboratories) and one PLgel mixed-C column were used in combination. The newly replaced columns were all mixed bed type columns, and polystyrene was used as a gel permeation chromatography standard material (GPC standard material).

2) Mooney Viscosity (MV, ML1+4, @ 100°C) (MU) Value For each polymer, Mooney viscosity (ML1+4, @ 100°C) (MU) was measured. The sample used at this time was left at room temperature (23 ± 5 ° C.) for 30 minutes or more, then 27 ± 3 g was taken and placed in the die cavity, and a platen was operated to apply torque. Mooney viscosity was measured.

On the other hand, the sample for Mooney viscosity measurement of the pre-modified polymer was heated with steam after part of the polymer was discharged from the reactor before adding the modifier in each of the examples and comparative examples. After removing the solvent by stirring it in hot water, it is obtained by hot roll drying to remove the remaining solvent and water. It was measured.

3) Beta value (β-value)
Measured using a D-RPA 3000 (rubber process analyzer) from Montech, frequency sweep range 0-100 Hz, static strain 3%, dynamic strain ) 0.25%, tan δ was measured at a measurement temperature of 100° C., and the slope of d (log (tan δ))/d (log (freq)) was shown as a beta value (β-value).

As shown in Table 1, Examples 1 to 4 containing a modifier-derived group having a specific structure at one end showed a significantly improved rate of increase in Mooney viscosity compared to Comparative Examples 1 to 4, and after modification, It can be confirmed that the beta value of the conjugated diene-based polymer of is also significantly lowered.

<Experimental example 2>
After producing a rubber composition and a rubber sample using the modified conjugated diene polymer produced in the above examples and comparative examples, and the unmodified conjugated diene polymer and modified conjugated diene polymer produced in the comparative example, The workability characteristics were measured by a method, and the results are shown in Table 2 below.

Specifically, the rubber composition comprises 100 parts by weight of each polymer, 70 parts by weight of carbon black, 22.5 parts by weight of process oil, 2 parts by weight of antioxidant (TMDQ), zinc oxide (ZnO ) and 2 parts by weight of stearic acid were blended to prepare respective rubber compositions. Thereafter, 2 parts by weight of sulfur, 2 parts by weight of a vulcanization accelerator (CZ) and 0.5 parts by weight of a vulcanization accelerator (DPG) are added to each rubber composition, and the mixture is heated at 50° C. for 1.5 minutes at 50 rpm. After mixing, a sheet of vulcanized compound was obtained using a roll at 50°C. The resulting vulcanized compounds were vulcanized at 160°C for 25 minutes to produce rubber samples.

1) cold flow (mg/min)
The cold flowability of each rubber sample was measured in an oven at 50°C using a cold flowability tester device. At this time, the cooling fluidity tester device consists of a copper holder welded on a support and a holder cap capable of covering the top of the copper holder. Specifically, the copper holder has a cylindrical shape with a diameter of 1.5 cm and a height of about 10 cm. A rubber sample of about 1 g is attached to the upper surface of this copper holder, and a holder cap weighing 318 g is attached from the top of the holder. Fasten in the direction of gravity. Here, the holder cap has a tubular shape with a height of about 10 cm and is closed with a copper material, and a hole with a diameter of about 5 mm is formed in the center of the closed upper surface. In addition, since the diameter of the holder cap is about 1.6 cm, which is larger than the diameter of the copper holder, the holder can be inserted into the tube of the holder cap when covering the upper part of the holder. A load that is the same as the weight of the holder cap can be applied. The cooled flow tester device with the rubber sample attached is then placed in an oven and left in the oven for about 30 minutes until the attached rubber sample reaches 50°C. At this time, the rubber sample flowing out through the hole formed in the holder cap of the tester device is removed at once with a sharp knife. After that, the step of cutting the rubber that has flowed out of the holder every 10 minutes and measuring the weight of the cut rubber is repeated three times, and the average value of the weight of the three times is calculated, and the average value is calculated. to calculate the weight of the rubber that flows out per unit time (minute). At this time, the larger the numerical value of the cold flow property, the poorer the storage stability.

2) Processability Processability is confirmed by measuring the Mooney viscosity (FMB, Final Master Batch) using the vulcanized compound and checking the difference in Mooney viscosity (ΔMV). indicates the difference (ΔMV, FMB-RP) between the Mooney viscosity of each polymer after modification and the Mooney viscosity of the formulation shown in Table 1. The smaller the difference in Mooney viscosity, the better the processability. It shows that it is superior to

Specifically, Mooney Viscosity (ML1+4 @ 100°C) (MU) was measured using each of the vulcanized formulations prepared above. The Mooney viscosity (MV) was measured at 100° C. with a Rotor Speed of 2±0.02 rpm using a Monsanto MV2000E Large Rotor. The sample used at this time was left at room temperature (23 ± 5 ° C.) for 30 minutes or more, then 27 ± 3 g was taken and placed in the die cavity, and a platen was operated to apply torque. Mooney Viscosity (FMB) was measured.

As shown in Table 2, it can be confirmed that Examples 1 to 4 are remarkably superior in workability as compared to Comparative Examples 1 to 4, and have greatly improved cold flow characteristics.

Claims (7)

1) polymerizing a conjugated diene-based monomer in the presence of a catalyst composition containing a rare earth metal compound to prepare an active polymer to which an organic metal is bound;
2) A method for producing a modified conjugated diene-based polymer, comprising reacting the active polymer with a modifier represented by Formula 2 below.

[In the chemical formula 2,
A is a hydrocarbon entity having 2 to 12 carbon atoms or a hydrocarbon entity having 2 to 12 carbon atoms containing one or more heteroatoms selected from N or O;
R _x is hydrogen or a methyl group;
n is an integer from 2 to 6; ] The hydrocarbon unit having 2 to 12 carbon atoms is represented by the following chemical formula 3, and is a hydrocarbon unit having 2 to 12 carbon atoms containing at least one heteroatom selected from N or O. 2. The method for producing a modified conjugated diene-based polymer according to claim 1 , wherein the body is any one of units represented by the following chemical formulas 4-1 to 4-4.
[Chemical Formula 3]
*-R _a1 -*
In the chemical formula 3,
R _a1 is a linear or branched alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms,
* is the position where the (meth)acrylate of Formula 2 is bonded;
[Chemical Formula 4-1]
(R _b1 ) ₃ C-R _b2 -OR _b3 -C(R _b4 ) _m1 (R _b5 ) _3-m1
In the chemical formula 4-1,
R _b1 and R _b4 are each independently an alkyl group having 1 to 5 carbon atoms, and the (meth)acrylate of chemical formula 2 is bonded to the end,
R _b2 and R _b3 are each independently an alkylene group having 1 to 5 carbon atoms,
R _b5 is a hydroxy group,
_m1 is an integer from 1 to 3;
[Chemical Formula 4-2]
C(R _c1 -OR _c2 ) _m2 (R _c3 ) _4-m2
In the chemical formula 4-2,
R _C1 is an alkylene group having 1 to 6 carbon atoms,
R _C2 is an alkyl group having 1 to 6 carbon atoms, and the (meth)acrylate of chemical formula 2 is bonded to the end,
R _c3 is hydrogen or an alkyl group having 1 to 6 carbon atoms,
_m2 is an integer from 1 to 4;
[Chemical Formula 4-3]
C(R _d1 ) _m3 (R _d2 ) _4-m3
In the chemical formula 4-3,
R _d1 is an alkyl group having 1 to 6 carbon atoms, and the (meth)acrylate of the chemical formula 2 is bonded to the end,
R _d2 is a hydroxy group or an alkyl group having 1 to 6 carbon atoms,
_m3 is an integer from 1 to 4;

In the chemical formula 4-4,
R _e1 to R _e3 are each independently an alkylene group having 1 to 5 carbon atoms,
* is the position where the (meth)acrylate of Formula 2 is bonded. The modifiers include dipentaerythritol hexaacrylate, dipentaerythritol hydroxypentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, propoxylated glycerol triacrylate, trimethylolpropane ethoxylate triacrylate, 1, 6-hexanediol diacrylate, 1,4-butanediol diacrylate, 1,2-ethanediol diacrylate, neopentyl glycol diacrylate, 1,3-butanediol diacrylate, 1,4-phenylene diacrylate, tris ( 2-hydroxyethyl)isocyanurate triacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol hydroxypentamethacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, trimethylolpropane trimethacrylate, Propoxylated glycerol trimethacrylate, trimethylolpropane ethoxylate trimethacrylate, trimethylolpropane ethoxy trimethacrylate, 1,6-hexanediol methacrylate, 1,4-butanediol dimethacrylate, 1,2-ethanediol dimethacrylate, neopentyl one selected from the group consisting of glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-phenylene dimethacrylate, isocyanurate trimethacrylate, tripropylene glycol dimethacrylate, ethylene glycol dimethacrylate, and polyethylene glycol dimethacrylate; The method for producing a modified conjugated diene-based polymer according to claim 1 or 2 , comprising one or more. The method for producing a modified conjugated diene-based polymer according to any one of claims 1 to 3 , wherein the rare earth metal compound includes a neodymium compound represented by Chemical Formula 5 below.

[In Chemical Formula 5, R ₁ to R ₃ are each independently hydrogen or a linear or branched alkyl group having 1 to 12 carbon atoms. ] In the rare earth metal compound, in the chemical formula 5, R ₁ is a linear or branched alkyl group having 6 to 12 carbon atoms, and R ₂ and R ₃ are each independently a hydrogen atom, or Production of the modified conjugated diene-based polymer according to claim 4 , comprising a neodymium compound which is a linear or branched alkyl group having 2 to 8 carbon atoms, provided that R ₂ and R ₃ are not hydrogen at the same time. Method. The method for producing a modified conjugated diene-based polymer according to any one of claims 1 to 5 , wherein the catalyst composition contains a rare earth metal compound, an alkylating agent and a halogen compound. The method for producing a modified conjugated diene-based polymer according to any one of claims 1 to 6 , wherein the catalyst composition further contains a conjugated diene-based monomer.